CN1141658A - Wet pressed paper web and method of making same - Google Patents

Wet pressed paper web and method of making same Download PDF

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Publication number
CN1141658A
CN1141658A CN94194831A CN94194831A CN1141658A CN 1141658 A CN1141658 A CN 1141658A CN 94194831 A CN94194831 A CN 94194831A CN 94194831 A CN94194831 A CN 94194831A CN 1141658 A CN1141658 A CN 1141658A
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CN
China
Prior art keywords
paper web
paper
nip
web
woollen blanket
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Granted
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CN94194831A
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Chinese (zh)
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CN1070964C (en
Inventor
罗伯特·S·安普尔斯基
艾伯特·H·索戴
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Procter and Gamble Co
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Procter and Gamble Co
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
    • D21F11/006—Making patterned paper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24446—Wrinkled, creased, crinkled or creped
    • Y10T428/24455—Paper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
    • Y10T428/24595—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness and varying density
    • Y10T428/24603—Fiber containing component

Abstract

The present disclosure provides a wet pressed paper web (120B, 120C). The web has a first relatively high density region (1083) having a first thickness K, a second relatively low density region (1084) having a second thickness P, which is a local maximum, and a third region (1074) extending intermediate the first and second regions. The third region (1074) includes a transition region (1073) having a third thickness T, which is a local minimum. The present disclosure also provides a method of making a wet pressed web. An embryonic web (120) of papermaking fibers is formed on a foraminous forming member (11), and transferred to a foraminous imprinting member (219) to deflect a portion of the papermaking fibers in the embryonic web (120) into deflection conduits (230) in the imprinting member (219). The intermediate web (120A) and the imprinting member (219) are then pressed between first and second dewatering felts (320, 360) in a compression nip (300) to further deflect the papermaking fibers into the deflection conduit (230) in the imprinting member (219) and to remove water from both sides of the web (120A). The imprinting member (219) is provided with a continuous flat web contact surfaces (220) to make wet pressed webs (120A, 120B) which have continuous net regions (1083) with high density and fornixs (1084) with low density, the web contact surfaces are distributed in the whole net regions (1083) with high density.

Description

Wet pressed paper web and manufacture method thereof
The part of the present patent application U.S. Patent application 08/170,140 that to be people such as Ampulski submit December 20 in 1993 continues.
The application relates to paper technology, specifically, and the method that relates to a kind of wet pressed paper web and make this paper web.
Some products that can dispose for example face-cloth, sanitary napkin, paper handkerchief and analog are generally all made by one or more paper webs.If want to allow these products get a desired effect, the paper web of making them must have some physical characteristic.Important in these characteristics is intensity, flexibility and absorbability.Intensity is the ability that paper web in use keeps its complete form.Flexibility is meant as the user paper is held in the hand, and when contacting each position of its health with paper web, the comfortable impression that the user obtains.Along with reducing of paper web stiffness, flexibility generally can increase, and absorbability is meant that it can draw and keep the characteristic of fluid.In general, when sacrificing some intensity of paper web, its flexibility and/or absorbability can be improved.Like this, just produce a kind of papermaking process.Promptly when making paper web have desirable strength characteristics, give its better flexibility and absorbability as far as possible.
Authorize in people's such as Sanford the United States Patent (USP) 3,301,746 and disclose a kind of paper web, it is predrying that it adopts a kind of Tad system that paper web is carried out heating power.Part paper web is coupled with the colored type in a kind of fabric joint on drying drum, the purpose of people's such as Sanford processing method is to improve its flexibility and absorbability, and don't sacrifice TENSILE STRENGTH, yet this air penetration formula drier that uses people such as Sanford anhydrates need very high energy, therefore just very expensive.
The United States Patent (USP) 3,537,954 of authorizing Justus discloses a kind of paper web, and this forms between a top fabric and the bottom forming net.In a nip, paper web is sandwiched in fabric and than between softness and the flexible felt of tool, thereby makes paper web have a kind of colored type.Authorize to disclose in people's such as Hulit the United States Patent (USP) 4,309,246 a kind of uncompacted wet web is delivered to one by weaving opening on the net impression fabric that element constitutes, in first nip, paper web is clipped between felt and the impression fabric squeezes.Then, impression fabric is being carried paper web is sent to drying drum from first nip second nip.The United States Patent (USP) 4,144,124 of authorizing people such as Turunen discloses a kind of paper machine.It has a pair of net former, and this former has a pair of endless fabric, and this fabric can be a woollen blanket.Article one, endless fabric is taken to press section with paper web.Press section can comprise the endless fabric that paper web is taken to press section, also has an other endless fabric, and it can be a woollen blanket, also comprises a silk screen to the paper web embossing.
Be that people such as Justus or Hulit exist a shortcoming, promptly they only use a woollen blanket when nip squeezes wet web.In the expressing process to paper web, water is that two sides from paper web are extruded, like this, in the exit of nip, never with the contacted paper of woollen blanket on the water of discharging just may reenter in the paper web.Just reduced the water separation capability of this pressing device in this rewetting phenomenon of nip exit paper web, influenced the bonding action between the fiber and fiber in the expressing process, and cause in nip densification a part of paper web bulk again.
People such as Turunen disclose a kind of nip, it comprises two endless fabrics, this fabric can be a woollen blanket, also comprise an impression net, but, people such as Turunen enter nip at paper web and paper web are not transferred on the impression fabric from a forming net before squeezing, so that make wet web produce a kind of initial deflection portion that extend in the impression fabric.Therefore, the paper web of Turunen method manufacturing is plane in the import department of nip basically, in nip, and the comprehensive compacting of paper web.This comprehensive compacting of paper web is very disadvantageous, because it has improved in the paper web density than the low-density part, thereby has limited the density variation between the paper web different piece.
In addition, in the pressing devices that the people adopted such as people such as Hulit and Turunen, its impression fabric has the compacting joint of some dispersions, is for example weaving the topped point that the warp of yarn, broadwise infall produce.The compacting point of this dispersion can not make wet embossed paper have a kind of continuous high-density region, so that bear load, does not also have the low density area of dispersion, so that its absorbent properties are provided.
Embossing can be used for making paper web to produce bulkiness, but might influence the bonding action between the fiber in the paper web for the embossing of paper web, because this bonding is to establish through the drying of paper web after forming.After the paper web drying, the fiber that moves along the direction perpendicular to the paper web plane can influence interfibrous associative key, thereby the TENSILE STRENGTH of paper web is lower than before the embossing.
Following list of references discloses embossing: european patent application 0499942A2, and United States Patent (USP) 3,556,907,3,867,225,3,414,459, and 4,759,967.
As a result, the papermaking expert proceeds research, so that the structure of paper is improved, makes it more economical, and improves its intensity again not sacrificing flexibility and absorbefacient while.
Purpose of the present invention just provides a kind ofly dewaters and the method for mold pressing to paper web.
Second purpose of the present invention is to improve a part of paper web tentatively to deflect in the impression element and go, and then this non-planar paper web and the impression element that generates squeezed between two deformable water adsorbent element.
The 3rd purpose of the present invention provides a kind of squeezing paper web, and for a given paper web flexibility, it has higher intensity.
The 4th purpose of the present invention provides a kind of paper web that has certain flower type of non-embossing, it has a highdensity continuous net-shaped zone, also have a series of low-density domes that are dispersed throughout in the whole continuous net-shaped district, also have the less transition range of thickness, it is lived each low-density dome circle at least in part.
The invention provides and a kind of paper web is carried out mold pressing and dehydration method.According to one embodiment of present invention, a kind of initial sheet forming that is made of paper fibre is on the forming element of a porous, then it is transferred on the impression element, a part of paper fibre in the initial paper web is deflected in the deflected channel of impression element, and the density of initial paper web does not increase.Then paper web and impression element are clipped in first and second dehydration and enter nip press between woollen blanket so that make paper fibre further go into to impress partially in the deflected channel of element, and from two sides of paper web with moisture removal.By preventing in the nip the first dehydration woollen blanket, and prevent rewetting, this compression-molded structures of paper web is preserved at nip exit paper web to by a narrow margin shear action.The present invention also provides a kind of method that wet web is carried out mold pressing, by between the porous impression element that has continuous net-shaped paper web impression face dehydration woollen blanket and wet web being squeezed, and produces the webbed region of a continuous densification.
Method of the present invention can comprise the following steps: to prepare a kind of aqueous dispersions of paper fibre; Prepare the forming element of a porous; Prepare one first dehydration woollen blanket; Prepare one second dehydration woollen blanket; Between first and second counter surface, form a nip; Prepare the impression element of a porous, it has the first paper web contact-making surface and the second woollen blanket contact-making surface, and first mask has a paper web stamping surface and a deflected channel part.This method also comprises: make paper fibre form a kind of initial paper web on porous formed element; Initial paper web is transferred on the porous impression element from porous formed element; Make a part of paper fibre in the initial paper web go into to impress partially in the deflected channel of element first surface, the moisture in the initial paper web is removed by deflected channel, to form a kind of non-planar middle paper web that constitutes by paper fibre of not densification; A face of paper web is near the first surface of porous impression element in the middle of making; Make the first dehydration woollen blanket another surface near middle paper web; Make second dehydration woollen blanket and the deflected channel portion fluid communication; In nip, middle paper web, porous impression element and first and second dehydration woollen blanket are squeezed, paper fibre is further gone in the deflected channel partially.Make the middle paper web densification of a part, remove moisture from two sides of middle paper web simultaneously, thereby form a mold pressing paper web.
Paper structure of the present invention comprises the paper web of a non-embossing, and it has one first higher density district, and its first thickness is K, and one second its second thickness is P than low density area, and it is a local maximum, is greater than the first thickness K.This paper structure also comprises one the 3rd district, and it extends between first and second district.The 3rd district comprises a transition range near first district.The 3rd thickness of transition range is T.Thickness T is a local minimum, is less than thickness K.This paper structure has a thickness that records than P/K, and this is worth greater than 1.0, also has a thickness that records than T/K, and this is worth less than 0.90.This paper web is for a given flexibility, and its intensity improves to some extent.
In a preferred embodiment, thickness than T/K less than 0.80, less than 0.70 better, best less than 0.65.Thickness is at least 1.5 than P/K, is at least 1.7 better, is at least 2.0 best.
In one embodiment, has one first higher density district by a narrow margin, continuous net-shaped district, and one second than low density area, this district comprise several dispersion than the low-density dome, or backing plate portion, they are distributed in whole continuous net-shaped district, and its height is different with continuous net-shaped district.Than being separated out by continuous net-shaped between the low-density dome,
Extend between continuous net-shaped district and each are than the low-density dome in the 3rd district, and it comprises a transition range, and transition range partly encloses near continuous net-shaped district and to each low-density dome of major general.
Specification is conclusion with claims, and claims are then specifically noted and drawn a clear protection scope of the present invention.By the following explanation of being done in conjunction with the accompanying drawings, people will have clearer understanding to the present invention.In the accompanying drawings, substantially the same element marks with same label.
Accompanying drawing 1 is the schematic diagram of the embodiment of a kind of continous mode paper machine that can use for the present invention, it has represented that paper web turns to the process of porous impression element from a porous formed element, and porous impression element carries paper web and enters nip, and paper web is attached on the porous impression element and is squeezed between first and second dehydration woollen blanket in nip.
Fig. 2 is the floor map of porous impression element, this element has one first paper web contact-making surface, it comprises the continuous net-shaped paper web stamping surface that has colored type that is plane on the macroscopic view, in porous impression element, have some dispersions, disjunct, the deflected channel do not linked up mutually.
Fig. 3 is the partial sectional view of porous impression element being done along 3-3 line among Fig. 2.
The enlarged diagram that Fig. 4 does nip among Fig. 1, it has expressed first a dehydration woollen blanket near the paper web first surface, impress the paper web contact-making surface of element near the porous of paper web second surface, and the second dehydration woollen blanket that impresses the element second woollen blanket contact-making surface near porous, wherein, porous impression element, woollen blanket and paper web all have been exaggerated with respect to the pressure roller of nip.
Fig. 5 is the floor map of porous impression element, and this element has a paper web contact-making surface, and it comprises a continuous deflected channel that colored type is arranged, and this passage has limited the paper web stamping surface of the mutual isolation of several dispersion.
Fig. 6 is a floor map of utilizing the mold pressing paper web of the porous impression element production shown in Fig. 2 and 3.
Fig. 7 is the generalized section of the paper web done along 7-7 line among Fig. 6.
Fig. 8 is the amplification profile of paper web shown in Figure 7.
Fig. 9 is the schematic diagram with porous impression element of a semi continuous paper web stamping surface.
Figure 10 is under different web speed, the curve that concerns between paper web dehydrating amount and the nip pressure, and this moment, paper web and impression element were at the nip pressurized, nip only has a dehydration woollen blanket, it is near paper web, and a straight empty roller is near woollen blanket, and a solid roll is near the impression element.
Figure 11 is under different web speed, dehydrating amount in the paper web and the relation curve between nip pressure, and paper web and impression element were clipped between the two dehydration woollen blankets and entered nip this moment.
Figure 12 is another embodiment of paper machine of the present invention, and wherein, when paper web is carried when a nip is sent to a Yang Keshi drying drum by the impression element, a dehydration woollen blanket nestles up the impression element.
Figure 13 A is another embodiment of paper machine of the present invention, and it has a compound impression element, and this element comprises a porous paper web flower type layer of being made by photopolymer, and this layer combines with the surface of a dehydration woollen blanket layer.
Figure 13 B is the amplification profile of compound impression element, and this element has the paper web flower type layer of a photopolymer, and this layer combines with the surface of a woollen blanket layer.
Figure 14 is the cut-away section light micrograph of a paper web, and it has represented the measuring method to thickness.
Figure 15 is the photo that adopts the paper web that paper machine shown in Figure 12 makes, and it shows that than the low-density dome by the preshrunk of wrinkling institute, this dome is distributed in the continuous net-shaped district of higher density.
A Figure 16 and the corresponding part of paper web shown in Figure 15 are through the section light micrograph of wrinkling paper web, and it adopts the paper machine of Figure 12 to produce, and the figure illustrates by the lower density dome of preshrunk with by the continuous continuously webbed region of the higher density of preshrunk.
Figure 17 is the photo of the paper web of the manufacturing of paper machine shown in Figure 13 A, and by preshrunk, dome is distributed in the continuous net-shaped district of higher density than the low-density dome for it.
Figure 18 is and the corresponding section light micrograph through wrinkling paper web of the paper web of Figure 17, and it is produced with the paper machine of Figure 13, it represented through preshrunk than low-density dome and the continuous net-shaped district of higher density.
Fig. 1 has expressed a specific embodiment that can be used for implementing continuous paper machine of the present invention.Method of the present invention comprises step or the operating process that several carry out continuously, although method of the present invention is preferably carried out in a continuous manner, should want clear and definite the present invention also can comprise the mode of batch operation, for example a kind of process of handmade paper.Below described be a kind of preferred sequence of steps, but should be appreciated that protection scope of the present invention depends on the content of appending claims.
In one embodiment of the invention, on the forming element 11 of a porous, formed a kind of initial paper web 120 that constitutes by paper fibre by a kind of aqueous dispersion of paper fibre.This initial paper web 120 promptly is sent to the impression element 219 of a porous subsequently, and this element has one first paper web contact-making surface 220, and it comprises a paper web stamping surface and a deflected channel part.A part of paper fibre in the nascent paper web 120 turns in the deflected channel portion of porous impression element 219, and paper web has formed a kind of middle paper web 120A thus not by enrichment.
Middle paper web 120A is being carried by porous impression element 219, is sent to a nip 300 from porous formed element 11, and this nip is made of two opposed press surface of first and second mip rolls 322 and 362.In the middle of the first dehydration woollen blanket 320 is positioned at paper web 120A near, second 360 on the woollen blanket of dehydration be positioned at porous impression element 219 near, middle paper web 120A and porous impression element 219 all are pressed into first, in the nip 300 between the two dehydration woollen blankets 320 and 360, so that making a part of paper fibre further is partial in the deflected channel portion of impression element 219, make a part middle paper web 120A enrichment relevant with the paper web stamping surface, by two side drainings paper web is further dewatered from paper web, generate a kind of mold pressing paper web 120B thus, it is more drier than middle paper web 120A.
Pass after the nip 300, mould district paper web 120B just is carried on the porous impression element 219.This mold pressing paper web 120B can carry out predrying in an air dryer 400, promptly allow hot-air at first pass the mold pressing paper web, and then pass porous impression element 219, thereby make mold pressing paper web 120B obtain further drying, the paper web stamping surface that porous can be impressed element 219 then is pressed among the mold pressing paper web 120B, for example can between pressure roller 209 and drying drum 510, carry out in the formed nip, thereby generate a kind of impression paper web 120C.When being pressed into the mold pressing paper web, the paper web stamping surface can make that part of paper web further enrichment relevant with this paper web stamping surface.Impression paper web 120C is dried on drying drum 510, and is wrinkling by a scraper 524 then.
If examine these method steps of the present invention in more detail closely, then in implementing first step of the present invention, a kind of aqueous dispersions of paper fibre at first is provided, it is converted by wood pulp, so that make initial paper web 120, is used for paper fibre of the present invention and generally includes the fiber that those are converted by wood pulp, the fiber of some other cellulose fibre slurry, cotton fiber for example, bagasse etc. also can be used, and are included in the scope of the present invention.Synthetic fiber, artificial fibre for example, polyethylene and polypropylene fibre etc. also can use with native cellulose fibre.(Wilmington, the Pulpex that Delaware) provides by Hercules Inc can be provided a kind of polyethylene fiber that plays the example effect TMOperable wood pulp comprises chemical pulp, kraft pulp for example, and sulfite pulp and sulfate pulp also comprise mechanical pulp, ground wood pulp for example, hot mechanical pulp also has the hot mechanical pulp through chemical modification.Also can use the slurry of making by wealthy page or leaf this (following also be called " hardwood ") and needlebush (following also be called " cork ").The fiber of being made by recycled writing paper also can be used for the present invention, wherein can contain above-mentioned any or all types of fibers, also can contain some other non-fiber substance, for example filler that uses in original papermaking and adhesive.
Except paper fibre, the papermaking batching that is used for forming the toilet paper structure also may adopt other interpolation composition or material, wherein some is known in the art, some after may being will be by cognition, and the type of these additives depends on the specific final use of the thin paper sheet of being expected.For example, for lavatory paper, paper handkerchief, face tissue and some other similar products, having higher wet strength is desired a kind of character, and therefore, people always wish to dose the chemical substance of some papermaking batching classes known in the art as " wet strong " resin use.
The general paper of the type of the relevant wet strengthening resin that uses in paper can be checked the monograph separate edition No.29 of TAPPI, " wet strength of paper and cardboard, the technical relation of pulp and paper industry " (New York, 1965).The most useful wet strengthening resin generally is cationic.Polyamide-epoxy chloropropionate ring (Polyamide-epichlorohydrin) resin belongs to cationic wet strengthening resin, it is found that its particularly suitable.The type of these suitable resins is given in the love on October 24th, 1972 and on November 13rd, 1973 to be had illustratedly in the United States Patent (USP) 3,700,623 and 3772,076 of Keim, this paper draws it and is reference.A commercial source of polyamide one epichlorohydrin resins that is suitable for is Hercules, Inc, and Wilmington, Delaware, its commodity are called Kymeme TM557H.
It is a kind of useful wet strengthening resin that polyacrylamide (Polyacrylamide) resin also has been construed to.These resins are authorized people's such as Coscia United States Patent (USP) 3,556,932 on January 19th, 1971, and authorize on January 19th, 1971 in people's such as Williams the United States Patent (USP) 3,556,933 and describe to some extent, and they are used as reference at this.A commercial source of polyacrylamide resin is American Cyanamid Co.Stanford, Connecticut, and its trade name is Parez TM631NC.
Ureaformaldehyde and melamino-formaldehyde also are to be well suited for some other water-soluble cationic resin that the present invention uses.The more common functional group of this multi-functional resins is a nitrogen-containing functional group, for example amino and the methylol that links to each other with nitrogen.The resin of polyethyleneimine: amine also is suitable for the present invention.In addition, temporary wet strengthening resin, for example Caldas 10 (Japanese Carlit produces) and CoBond 1000 (National Starch and Chemieal Company production) also can be used for the present invention.Should be appreciated that compound with above-mentioned wet strengthening resin and temporary wet strengthening resin and so on adds to goes in the intermittent pulp proportioning to choose wantonly, for enforcement of the present invention and nonessential.
Initial paper web 120 is preferably produced in the aqueous dispersions by paper fibre, though will also be operable in the liquid of fiber dispersion outside water.Fiber concentration of formed dispersion liquid in water is approximately 0.1-0.3%.The percentage concentration of so-called dispersion liquid, paper pulp, paper web or other system is meant the total amount of the weight of dried fiber in this system divided by this system, multiply by the numerical value of 100 gained then.The weight of fiber always is meant the weight of bone dry fiber.
Second step of the present invention is the initial paper web 120 that forms a kind of paper fibre.A kind of aqueous dispersions of paper fibre is delivered to a head box 18.This case can be any head box that makes things convenient for form that has.The aqueous dispersions of paper fibre is sent to the forming element 11 of a porous by head box 18, to form initial paper web 120.This forming element 11 can be a kind of continuous fourdrinier wire.This porous formed element 11 also can be a kind of by a plurality of protuberance polymer formed continuous enhancing structure that connects together, can generate a kind of initial paper web 120 with it with two or more a plurality of different basis weights zone, for example authorized people's such as Trokhan United States Patent (USP) 5 on September 14th, 1993,245, described in 025 like that, this patent is used as reference at this.
Though expression is a kind of single forming element 11 in Fig. 1, single net or two net former all are operable.The forming net device of other kinds, for example S or C reel or structure can be used.
Forming element 11 is by the supporting of breast roll 12 and a plurality of slewing rollers, only shows two slewing rollers 13 and 14 wherein in Fig. 1.Under the drive of a driving mechanism (not shown), forming element 11 moves along the direction shown in the arrow 81.Dispersion liquid is discharged on the porous formed element 11, removes portion of water liquid medium wherein, the aqueous dispersions of paper fibre can be made initial paper web 120.This initial paper web 120 have one with multihole device 11 contacted first paper surface 122 and second paper surface that is positioned at opposite side.
This initial paper web 120 can be made by a continuous paper-making process, as shown in Figure 1, also can carry out step by step in batches, for example can adopt the handmade paper manufacturing technique.After the aqueous dispersions of paper fibre deposits on the porous formed element 11, adopt this field technique known portion of water wherein can be removed by diffusing liquid medium, thereby form initial paper web 120.Vacuum tank, forming board, dewatering plate and similar device can be with the moisture removals in the aqueous dispersions on the porous formed element 11.Initial paper web 120, is sent near the porous impression element 219 around slewing rollers 13 operations with forming element 11.
Porous impression element 219 has one first paper web contact-making surface 220 and one second woollen blanket contact-making surface 240.Paper web contact-making surface 220 has a paper web stamping surface 222 and a deflected channel portion 230, shown in Fig. 2 and 3.This deflected channel 230 forms at least a portion continuous passage, and they lead to second surface 240 from first surface 220, so that make moisture pass porous formed element 219.Like this, when moisture was discharged from the paper web of paper fibre along the direction of porous impression element 219, these moisture just can break away from paper web and can not contact with it again.This porous impression element 219 can comprise a kind of endless belt as shown in Figure 1, and this band is by a plurality of roller 201-217 supportings.By means of a drive unit (not shown), can make porous impression element 219 along the operation of the direction shown in 281 among Fig. 1.The first paper web contact-making surface 220 of porous impression element 219 can spray a kind of emulsion, and this emulsion contains the water of 90% weight of having an appointment, 8% oil, 1% hexadecanol and about 1% surfactant, for example Adogen TA-100.This emulsion helps paper web from the transfer of impression element 219 to drying drum 510.Certainly, should be clear and definite, if when adopting the technology of batch production to make handmade paper, porous impression element 219 does not need to comprise the endless belt.
As an embodiment of porous impression element 219, it can comprise a kind of fiber band that forms of being weaved by long filament.This paper web stamping surface 222 can be made of the joint of the formed some dispersions in crosspoint of weaving long filament.As the suitable filament fiber band of weaving that porous impression element 219 uses, authorize people's such as Sanford United States Patent (USP) 3,301 on January 31st, 1967,746, authorized the United States Patent (USP) 3,905,863 of Ayers on September 16th, 1975, authorized the United States Patent (USP) 4 of Trokhan on March 4th, 1980, authorized the United States Patent (USP) 4,239 of Trokhan on December 16th, 191,609 and 1980, all have disclosedly in 065, above-mentioned patent is used as reference at this.
In another embodiment shown in Fig. 2 and 3, the first paper web contact-making surface 220 of porous impression element 219 comprises the continuous net-shaped paper web stamping surface 222 with certain colored type that is the monoplane on the macroscopic view.This continuous net-shaped paper web stamping surface 222 has formed deflected channel 230 some dispersions, mutually unrelated, no serial relation on this porous impression element 219.These deflected channel 230 have opening 239, its shape and to distribute all be random, but preferably with a kind of previously selected shape of unification and distribution mode repeated arrangement on the first paper web contact surface 220.This continuous net-shaped paper web stamping surface 222 and the deflected channel 230 of disperseing, for forming a kind of paper structure that has continuous, higher density webbed region 1083 and be distributed in the some more low-density dome 1084 within this highly dense webbed region 1083 is of great use, shown in Fig. 6 and 7.
The suitable shape of opening 239 includes, but are not limited to circle, ellipse and polygon, hexagonal apertures 239 as shown in Figure 2.This opening 239 can be very regular, has uniform spacing in direction anyhow.But also can make opening 239 go up interlaced opening in machine direction (MD) and cross-machine direction (CD), as shown in Figure 2, machine direction wherein parallels with the direction that paper web passes equipment moving, and cross-machine direction is meant the direction perpendicular with machine direction.Can make a kind of porous impression element 219 according to the following United States Patent (USP) that is incorporated by reference, make it to have the mutual disjunct deflected channel 230 of a continuous netted paper web stamping surface 222 and some dispersions, these patents are: the US that authorized people such as Johnson on April 30th, 1985,4,514,345, authorized the US of Trokhan on July 16th, 1985,4,529,480, and on March 24th, 1992 authorize people's such as Smurkoski US, 5,098,522.
With reference to Fig. 2 and 3, this porous impression element 219 can comprise a woven enhancing element 243, is used for to 219 humidifications of porous impression element.This enhancing element 243 can comprise the enhancing yarn 242 of machine direction and the enhancing yarn 241 of cross-machine direction, and certainly, any suitable fabric flower type all is operable.That these are formed by the space between yarn 241 and 242, be present in and weave the opening that strengthens in the element 243, size than the opening 239 of deflected channel 230 is smaller, the opening in the woven enhancing element 243 and the opening 239 of deflected channel 230 have produced one jointly and have stretched to the continuous passage of second surface 240 from first surface 220, so that make water pass porous impression element 219.This enhancing element 243 can also provide an area supported, so that the restriction fiber is gone into deflected channel 230 partially, prevents from again simultaneously to produce broken hole, for example more low-density dome 1084 with that part of paper web of deflected channel 230 associated.Such eye or pinprick may be to work as whole paper web upward pressure not simultaneously, and water or air flow cause when passing deflected channel.
The area of paper web stamping surface 222 accounts for about 15～65% of first contact surface, 220 gross areas, is preferably about 20～50%, can make the higher density district 1083 shown in Fig. 6 and 7 moderate with the ratio than the area of low-density dome 1084 like this.Size at the opening of plane, first surface 220 place intrinsic deflection passage 230 is considered effective free aperture.So-called effective free aperture is meant the numerical value of the area of first surface 220 place plane upper shed 239 divided by 1/4th gained of opening 239 girths.This effective free aperture should be 0.25～3.0 times of the paper fibre average length that forms initial paper web 120, is preferably its 0.5～1.5 times.The degree of depth of deflected channel 230 (Fig. 3) is between 0.1mm～1.0mm.
In another embodiment shown in Figure 5, porous impression element 219 can have one first paper web contact-making surface 220, and it comprises a deflected channel 230 with continuous colored type, and it is around some dispersions, paper web stamping surface 222 independently.Porous impression element 219 shown in Figure 5 can be used for making a kind of mold pressing paper web, and it has a continuous more low-density webbed region, also has the zone of the higher density of several dispersion, and they are distributed in the whole continuous low-density webbed region.Porous impression element 219 as shown in Figure 5 can be according to United States Patent (USP) 4,514,345 described manufacturings of authorizing people such as Johnson on April 30th, 1985, and this document is used as reference at this.
In another embodiment shown in Figure 9, porous impression element 219 can have one first paper web contact-making surface 220, and it comprises several semi-continuous paper web impression faces 222.At this, as long as several impression faces 222 are arranged along the continual basically extension of any one direction of paper web contact-making surface 220, and each stamping surface is isolated with adjacent stamping surface 220 by a deflected channel 230, and then the colored type of paper web stamping surface 222 just is counted as semi-continuous.Paper web contact-making surface 220 shown in Figure 9 has some adjacent semicontinuous stamping surface 222, and they are by 230 intervals of semi-continuous deflected channel.These semi-continuous stamping surface 222 can be extended along the direction that is roughly parallel to machine direction or crosses machine, also can be along extending with machine direction or cross-machine direction direction at an angle, as shown in Figure 9.On August 26th, 1992 was 07/936 by the application number that people such as Ayers submit to, 954, the name be called " have the making paper web of semicontinuous colored type and manufacturing thus paper " U.S. Patent application be used as reference at this so that the making paper web with semicontinuous colored type is described.
The 3rd step of the present invention comprises transfers to porous impression element 219 with initial paper web 120 from porous formed element 11, the second paper web face 124 is placed on the first paper web contact-making surface 220 of porous impression element 219.The 4th step of the present invention comprises in the deflected channel portion 230 that makes a part of paper fibre deflection paper feed width of cloth contact-making surface 220 in the initial paper web 120, and by deflected channel 230 moisture is excluded from initial paper web 120, to form a kind of middle paper web 120A of paper fibre.The initial concentration of paper web at the branchpoint place is preferably in about 10～20%, so that paper fibre is to 230 deflections of deflected channel part.
Initial paper web 120 a part of paper fibre in stage that impresses element 219 transfers and paper web 120 can apply a fluid pressure differential to initial paper web 120 at least in part and carry out to the deflection stage of deflected channel portion 230.For example, initially 120 can turn to impression element 219 by forming element 11 by a narrow margin,, perhaps also can be undertaken by a rotary paper vacuum furnace (not shown) that picks up as passing through a vacuum tank 126 among Fig. 1 by vacuum action.The pressure reduction of initial paper web two sides that provided by vacuum source (for example vacuum tank 126) makes fiber deflection deflected channel portion 230, and preferably by this deflected channel portion 230 moisture is discharged from paper web, so that the concentration of paper web is brought up to about 18～30%.The pressure reduction of initial paper web 120 2 sides can (be about 4～12 Inches Of Mercuries) between 13.5kpa～40.6kpa.The vacuum that vacuum tank 126 is provided can make initial paper web 120 go to porous impression element 219, and makes fiber deflection deflected channel portion 230, and don't with initial paper web 120 compactings.In the additional vacuum boxes (not shown) also can be included in, so that the moisture among the paper web 120A in the middle of further removing.
With reference to accompanying drawing 4, at the upstream end of nip 300, paper web 120A goes in the deflected channel 230 partially in the middle of the part, thereby makes this centre paper web 120A become non-monoplane property.Shown middle paper web 120A has roughly, and homogeneous thickness (is first and second paper web face 122 in the upstream of pressure surface 300,124 distance), paper web 120A had turned in the impression element 219 in the middle of this showed a part, but did not make the local enrichment of middle paper web 120A or the compacting of nip 300 upstreams.The deflection of fiber in the logical portion 230 of deflection can be finished basically simultaneously in the transfer of initial paper web 120 and the initial width of cloth.The above-mentioned US.4 that is cited, 529,480 are cited again at this, so that how explanation to transfer to initial paper web on the multihole device, and a part of paper fibre in the initial paper web are deflected in the multihole device go.
The 5th step of the present invention is included in the nip 300 wet middle paper web 120A squeezed, to form mold pressing paper web 120B.With reference to Fig. 1 and 4, middle paper web is carried on the porous impression element 219 from porous formed element 11, and passes through by pressure roller 322 and 362 2 formed nips 300 of opposed press surface.As shown in the figure, the first dehydration woollen blanket 320 is bearing in the nip by pressure roller 322, and moves around several woollen blanket backing rolls 324 along direction 321.Equally, the second shown dehydration woollen blanket 360 is bearing in the nip 300 by pressure roller 362, and moves around a plurality of woollen blanket backing rolls 364 along direction 361.A kind of woollen blanket dehydration equipment 370, for example the Uhle vacuum tank can match with each woollen blanket 320,360 that dewaters, so that will drain from the moisture that middle paper web 120A changes over to the dehydration woollen blanket.
Pressure roller 322 and 362 can have very smooth generally mutual opposed press surface, but also can make pressure roller 322 and 362 have groove.(not shown) in an alternative embodiment, this pressure roller comprise the vacuum furnace of surface eye with holes, so that moisture is discharged from middle paper web 120A.Pressure roller 322 and 362 can have the opposed press surface that scribbles rubber, also a rubber strip can be arranged between each pressure roller and the contacted with it dehydration woollen blanket.Pressure roller 322 and 362 can comprise solid roll, and they have the rubber layer of a smooth skeleton hard (bonehard), or in pressure roller 322 and 362 one or two is a kind of groove pressure roller that has the hard rubber layer of a skeleton.
For the operating process to nip 300 describes, impression element 219 in Fig. 4, dewatering bands 320 and 360, and paper web is all with respect to pressure roller 322 and 362 and amplified.Though in Fig. 4 along the machine direction of nip 300 deflected channel 230 of only having drawn, should be clear and definite, in any one given moment, along all existing several deflected channel in the nip of machine direction.
" dehydration woollen blanket " described herein is meant a kind of element, it has water imbibition, compressible and have elasticity, so it can be out of shape with the profile of the middle paper web 120A of the on-plane surface state on the impression element 219, and can receive and hold the moisture that from middle paper web 120A, extrudes.Dehydration woollen blanket 320 and 360 can be by natural material, contains into material or the two and combines and make.
Dehydration woollen blanket 320 and 360 thickness are about 2mm～5mm.It quantitatively is about 800～2000g/m 2, averag density (quantitative/thickness) is about 0.35g/cm 3～0.45g/cm 3, gas permeability is about 15～110 feet 3/ minutes per foot 2, dehydration woollen blanket two side pressure differences are to record in 0.12KPa (0.5 inches of water(in H) time.Dehydration woollen blanket 320 preferably has a kind of first surface 325, and its density is bigger, and pore-size is less, also has a kind of second surface 327, and its density is less, and pore-size is bigger.Equally, preferably to have a kind of density big and first surface 365 and density that hole is less are less, the second surface 367 that hole is bigger for dehydration woollen blanket 360.The high density on the first woollen blanket surface 325,365, fine pore can extrude moisture rapidly from paper web in nip 300.And the low-density on the second woollen blanket surface 327,367, macrovoid can provide some spaces in the dehydration woollen blanket, so that be stored in the moisture that extrudes in the nip 300 from paper web.
Dehydration woollen blanket 320 and 360 should have 20～80% compressibility, is preferably 30～70%, and is better between 40～60%." compressibility " described herein is meant under a given load (below will define it), the percentage of dehydration woollen blanket varied in thickness.Dehydration woollen blanket 320 and 360 modulus of compressibility should be less than 10000psi, better less than 7000psi, better less than 5000psi, and best between 1000～4000psi, " modulus of compressibility " described herein is meant the ratio of variation with the change of dehydration woollen blanket thickness of load.The measuring method of compressibility and modulus of compressibility is as follows.The woollen blanket that will dewater is placed on the papermaking fabric, and this fabric is weaved by monofilament polyester and formed, and filament diameter is about 0.40mm, and on first direction, per inch is had an appointment 36 fibers and on the second direction vertical with first direction, per inch has about 30 fibers.They form a kind of square colored type of weaving.Under the situation that does not have pressure load, the thickness of papermaking fabric is about 0.68mm (0.027 inch).This papermaking fabric can be from Appleton Wire Company ofAppleton, and Wisconsin buys.The woollen blanket that will dewater location makes its common and close papermaking fabric of the contacted one side of paper web.Have a fixed tension force/compression tester that changes of weighing apparatus by a kind of then, for example can be by Instron Engineering Corporation of Canton, 4502 pairs of these woollen blanket one fabrics of the Instron Model that Mass buys are to compressing.This instrument has the presser feet of a circle, and its surface area is about 13cm 2(2.0 inches 2), it links to each other with a crosshead, and this crosshead is with 5.08cm 2The speed motion of/minute (2.0 inch per minute).At 0psi, 300psi, 450psi and 600psi load are measured the right thickness of woollen blanket one fabric down, and load wherein calculates with psi.The load point size that to be read by the load sensor of instrument obtains divided by the surface area of presser feet.Measure 0,300 450 and the 600psi load thickness of fabric down itself simultaneously respectively.Utilizing following equation to calculate with psi is the compressibility and the modulus of compressibility of unit:
Compressibility=100 * (TFP0-TP0)-(TFP450-TP450)/(TFP0-TP0)
Modulus of compressibility=(300psi) * (TFP300-TP300)/(TFP300-TP300)-(TFP600-TP600)
Wherein, TFP0, TFP300, TFP450, TFP600 is respectively woollen blanket one fabric at 0psi, 300psi, the thickness under 450psi and the 600psi load, TP0, TP300, TP450 and TP600 be respectively fabric this in 0psi, 300psi, the thickness under 450psi and the 600psi load.The dehydration woollen blanket 320 that be fit to use and 360 can Albany International Company of Albany, and New York buys, and its name is called SUPERFINE DURAMESH Style XY31620.
In nip 300, middle paper web 120A and paper web stamping surface are between the first and second woollen blanket layers 320 and 360.The first woollen blanket layer 320 is near the first surface 122 of middle paper web 120A, 222 second surfaces 124 near paper web 120A of paper web stamping surface.The second woollen blanket layer 360 can make the second woollen blanket layer 360 and deflected channel portion 230 realize fluid communication when being positioned at nip 300.
With reference to Fig. 1 and 4, when the first dehydration hair 320 during, in the middle of the first surface 325 of the first dehydration woollen blanket 320 is positioned near the first surface 122 of paper web 120A around pressure roller 322 operations.Equally, when the second dehydration woollen blanket 360 during around pressure roller 362 operation, the first surface 365 of the second dehydration woollen blanket 360 is positioned near the second woollen blanket contact-making surface 240 of porous impression element 219.Like this, when middle paper web 120A is with when passing nip 300 on porous impression fabric 219, middle paper web 120A, impression fabric 219 and first and second dehydration woollen blanket 320,360 are pressed together, between two relative roll surfaces of pressure roller 322 and 362.In the squeezing of 300 couples of middle paper web 120A of nip, make paper fibre further to deflected channel portion 230 intrinsic deflections that impress element 219, and moisture is further deviate from from middle paper web 120A, form mold pressing paper web 120B.The moisture of discharging from paper web is received and is stored in the dehydration woollen blanket 320 and 360.Moisture is to receive by the deflected channel portion 230 dehydrated woollen blankets 360 that impress element 219.
Entrance point at nip 300, the concentration of middle paper web 120A should be about 14～80%, better about 15～35%, has the paper fibre among a kind of so middle paper web 120A of suitable concn, the bonding action of fiber and fiber is less, again arrange than being easier to, under the effect of the first dehydration woollen blanket 320, be easy to go into partially within the deflected channel portion 230.
When middle paper web 120A passed through nip 300, its nip pressure preferably was at least 100 pounds/inch 2(psi), it is then better to be at least 200psi.In a preferred embodiment, the pressure of middle paper web 120A in nip 300 is between 200～1000psi.People wish with pound/inch 2Determine nip pressure, and do not adopt this linear pressure of pound/inch to represent that this is that linear pressure can't be taken the width of nip 300 into account because when along machine direction (MD among Fig. 4) when measuring.The width of nip 300 can change according to the dewater woollen blanket 320,360 and the character of impression element 219 and the surperficial stiffness of pressure roller 322 and 362.So, to measure nip pressure with the point size pressure of unit length and can not embody mensuration nip pressure, on the practical work, two kinds of different nips when measuring with linear pressure, may have identical pressure, but its pound force value per square inch is all different.
The nip pressure that with psi is unit is that pressure roller 322 and 362 is applied to radial load (pressure roller 322 and 326 pairs of radial load equal and opposite in directions that paper web applies, direction is opposite) on the paper web, calculates divided by the area of nip 300.The various power or the pressure sensor that can utilize this area people to know come the radial pressure that pressure roller 322 and 362 applies is calculated.For example, when pressure roller 322 and 326 when being hydraulically powered, the pressure of pressure roller hydraulic system can be used to calculate the radial load that is imposed on paper web by pressure roller 322 and 362 when pressure roller 322 and 326 combines.Can utilize a carbon paper and a blank sheet of paper to measure the area of nip 300, its length should be more than or equal to the length of pressure roller 322 and 362.Carbon paper is placed on the blank sheet of paper.By means of first and second dehydration woollen blanket 320,360 and impression element 219 carbon paper and blank sheet of paper are placed in the nip 300.Make carbon paper near the first dehydration woollen blanket 320, and blank sheet of paper is near impression element 219.Pressure roller 322 and 362 pressings mutually produce a desirable radial load, impose on impression vestige from paper by carbon paper, can measure the area that stands above-mentioned radial load in the nip 300.
After mold pressing paper web 120B was squeezed, its concentration was preferably about 30% in nip 300 exits.As shown in Figure 1, when middle paper web 120A is squeezed, under the mold pressing effect, paper web has first a higher density district 1083 that links mutually with paper web stamping surface 222, also has a paper web second that links mutually with deflected channel portion 230 than low density area 1084.It is to be plane but to have to be the continuous net-shaped paper web stamping surface 222 that certain spends type that impression fabric 219 has on the macroscopic view, the middle paper web 120A of squeezing is shown in Fig. 2-4 on impression fabric 219, mold pressing paper web 120B has been had on the macroscopic view be plane, be continuous net-shaped regional 1083 of certain flower type but have, this regional density is higher, also have dome 1084 some dispersions, that density is lower, they are distributed in the whole webbed region 1083 continuous, higher density.This mold pressing paper web 120B is shown in Fig. 6 and 7.The advantage of this mold pressing paper web is that its webbed region 1083 continuous, that density is higher provides a kind of continuous load path for the tension load that bears.
The characteristics of this mold pressing paper web 120B also are: it has density region 1074 in the 3rd, and it is between first and second zone 1083 and 1084, and the 3rd zone 1074 comprises a near transition range 1073 that is positioned at first high density area 1083.Should form when the first dehydration woollen blanket 320 sucks paper fibre in the deflected channel portion 230 by middle density region 1074, its cross section is the trapezoidal of convergent.This transition range 1073 is that it is surrounded middle density region 1074 owing to the compaction of middle paper web 120A on the periphery of deflected channel portion 230 forms, and is at least in part that each low-density dome 1084 is surrounded.The characteristics of this transition range 1073 are that it has a thickness T that is local minimum, and this thickness also has a local density less than the thickness K in higher density district 1083, and this density is greater than the density in higher density district 1083.More low-density dome 1084 thickness are P, and it is a local maximum, and this thickness is greater than the thickness K in the continuous net-shaped district 1083 of higher density.
Break away from concrete theory and do not talk, should admit, the effect of this transition range 1073 is equivalent to a folding, has improved the flexibility of paper web.
In Fig. 6-7, density region 1074 is all between high density webbed region 1083 and low-density dome 1084 in each, and density region 1074 all surrounds a low-density dome 1084 in each.In another embodiment, 219 pairs of paper webs of impression fabric are as shown in Figure 5 exerted pressure, make it to have one continuous low-density regional 1084, high density area 1083 several dispersion, that spread all over whole low density area 1084, also have some in density regions 1074.Density region 1074 is all between continuous low density area 1084 and high density area 1083 in each, and high density area 1083 is surrounded, and transition range 1073 then surrounds density region in each 1074.
The characteristics of the mold pressing paper web 120B that is made by process shown in Figure 1 are: when paper web quantitatively identical with thickness H (Fig. 8), it has higher draw tensile strength and flexibility.Why it has above-mentioned performance, and its reason is that partly cause is an existing density contrast between its high density area 1083 and the low density area 1084 at least.Owing between the first electric woollen blanket 320 of dehydration and paper web platen surface 220, paper web 120A in the middle of the part has been carried out squeezing and has formed high density area 1083, thereby the intensity of paper web is strengthened.The fiber that the compacting and the dehydration to the part paper web of carrying out simultaneously makes high density area forms fibre bundle, thereby can bear external load.Also formed transition range 1073 during squeezing, it provides flexibility for paper web.Low density area 1084 goes into to impress in the deflected channel portion 230 of element 219 partially, for paper web provides bulkiness, can strengthen its absorbent properties.In addition, during the paper web 120A of squeezing centre paper fibre is sucked deflected channel portion 230, formed middle density region 1074, thereby increased the macroscopic thickness H (Fig. 8) of paper web.The increase of web thickness H makes the apparent density of paper web reduce (paper web quantitatively divided by web thickness H).Along with its flexibility that reduces of paper web stiffness has just increased.
Its total TENSILE STRENGTH TT of paper web (by the maximum intensity of quantitative criterionization) that the present invention makes at least than correspondingly but without the base web of squeezing (, but in the nip 300 of two woollen blanket interlayers, not squeezing and the paper web that makes) raising about 15% with identical batching and impression element 219.Total TENSILE STRENGTH of the paper web that makes according to the present invention can reach about 300 meters at least.The paper web that the present invention makes has the stiffness index of standard, and it hangs down about 15% than the base web of corresponding not squeezing at least.The standard stiffness index TS/TT of paper web of the present invention is less than 10.In one embodiment, its total TENSILE STRENGTH TT of paper web that is made by the present invention is at least 1600 meters, and standard hardness index TS/TT is then less than 5.5.The paper web that makes according to the present invention, its macroscopic thickness H is at least about 0.10mm.In one embodiment, its macroscopic thickness of paper web constructed in accordance is 0.20mm, and preferably can reach more than the 0.30mm.Standard deflection index TS/TT represents is that the stiffness of paper web is carried out value after the standard by total TENSILE STRENGTH of paper web.Below will be to standard tensile intensity, the measuring method of standard stiffness index and macroscopic thickness H describes.
Density contrast between high density area 1083 and the low density area 1084 is a part because the initial paper web 120 of a part has advanced in the deflected channel portion 230 of impression element 219 partially causes, and it has caused a kind of middle paper web 120A of on-plane surface state at the upstream end of nip 300.A kind of plane paper web will be subjected to some uniform compaction force when being passed nip 300, thereby improve the minimum density of mold pressing paper web 120B.Non-planar middle paper web 120A in deflected channel portion 230 has avoided this uniform compaction, has therefore kept a kind of lower density.
The formation of the density contrast of high density area and low density area, partly cause are by the squeezing of first and second dehydration woollen blanket 320,360, two surfaces of moisture from paper web are excluded, and prevented that the change once more of paper web is wet.When middle paper web 120A in nip 300 during pressurized, moisture is drained on first and second paper surface 122,124.It is crucial that the moisture that paper web two faces are extruded is drained from its surface.Otherwise the moisture of extruding might reenter among the mold pressing paper web 120B in nip 300 exits.For example, if cancellation dehydration woollen blanket 360 enters water the deflected channel portion 230 from second paper surface 124, the deflected channel portion 230 by impression element 219 will reenter among the mold pressing paper web 120B in the exit of nip 300.
It is very disadvantageous that water reenters the mold pressing paper web, because this can reduce the concentration of mold pressing paper web 120B, thereby reduces dry efficient.In addition, moisture reenters mold pressing paper web 120B, will have influence on formed fiber associative key in middle paper web 120A pressurized process, and make paper web thinning.Especially moisture turns back to the associative key that will influence among the mold pressing paper web 120B in the high density area 1083, thereby reduces this regional density and anti-load-bearing capacity.Moisture returns to mold pressing paper web 120B can also influence the fiber associative key that constitutes transition range 1073.
Dehydration woollen blanket 320 and 360 has prevented to make the change again of mold pressing paper web wet by paper surface 122 and 124, thereby has been maintained high density area 1083 and transition range 1073.In certain embodiments, people wish in the exit of nip 300 the first dehydration woollen blanket 320 to be withdrawn the first surface 122 of mold pressing paper web 120B, the first surface 122 of paper web in case the moisture in the woollen blanket 320 that dewaters is got wet again.Equally, people also wish in the nip exit the second dehydration woollen blanket 360 to be withdrawn impression element 219, in case the moisture in the dehydration woollen blanket 360 reenters paper web by deflected channel portion 230.In the embodiment shown in Fig. 1 and 4, first and second dehydration woollen blanket 320,360 can be by roller 324 and 364 supportings, so that make it to follow hard on respectively the opposed press surface of pressure roller 322 and 362, like this, the dehydration woollen blanket just can not contact with mold pressing paper web 120B or impression element 219 at the downstream part of nip 300 outlets again.
The applicant has found that, when comprising in the nip that two dehydration woollen blankets 320 and 360 have many advantages when squeezing, be better than a dehydration woollen blanket is only arranged in the nip, for example the dewater situation of woollen blanket 320, also being better than only has a dehydration woollen blanket 320 in the nip, pressure roller 322 comprises the situation of the vacuum furnace on an eye with holes surface again simultaneously.The structure of straight empty roller than solid roll a little less than some, its squeezing is limited in one's ability under the pressure of higher-pressure region.The porous surface of vacuum furnace also may produce irregular pressure (for example the web pressure at the position in vacuum furnace surface eyelet district can reduce) to paper web, and causes the local rewetting of locating separately with eyelet in the paper web.The more important thing is that the dehydrating amount by vacuum furnace depends on the time of staying of paper web at nip.The speed that increases paper web can make paper machine produce more economically, but has shortened in the time that nip vacuumizes, thereby reduced vacuum furnace paper web is effectively dewatered.Especially the applicant has found when the nip that only has vacuum furnace with a dehydration woollen blanket and matches, along with the increase of web speed, the dehydrating amount of paper web reduces, and under higher web speed, along with the increase of nip pressure, dehydrating amount reduces reality.On the contrary, when adopting two dehydration woollen blankets, no matter increase nip pressure and still adopt high web speed, the dehydrating amount of paper web all can increase, and does not need to use vacuum furnace.
Curve among Figure 10 and 11 has represented to make by squeezing paper web between two dehydration woollen blankets and impression element the situation of dehydrating amount increase.Figure 10 shows the dehydrating amount (the moisture pound weight of deviating from every pound of dried fiber in the paper web) of paper web when the constant speed of paper web is 400～2000fpm (feet per minute) and the functional relation between the nip pressure psi.Curve among Figure 10 and 11 be web speed be 400,800 and the situation of 2000fpm under obtain.The straight line of 1000 and 1500fpm in Figure 10 and 11 be from web speed be 400,800 and the data of 2000fpm insert.The speed of paper web is meant the web speed along machine direction MD shown in Figure 4.Data among Figure 10 obtain in the following cases: a paper web is arranged in the nip, it is between a dehydration woollen blanket and an impression element, one solid pressure roller is positioned near the impression element, and vacuum furnace is near the dehydration woollen blanket, as can be seen from Figure 10, increase along with chart speed, the water yield of deviating from from paper web reduces, specifically, and when chart speed is higher than the 800fpm left and right sides, the dehydrating amount of paper web reduces with the increase of nip pressure, along with the dehydration rate of the increase paper web of nip pressure reduces.
Therefore, for making the paper web dehydration reach a desirable level, adopting the form of single dehydration woollen blanket nip to come the mold pressing paper web, still is that nip pressure all is restricted to web speed.
Data among Figure 11 come from nip arrangement mode shown in Figure 4, and its paper web and impression element all place between two dehydration woollen blankets, and one of them pressure roller 362 is solid, and another pressure roller 322 is with grooves.Used when being used for obtaining the dehydration woollen blanket of Figure 11 data and impression element with acquisition Figure 10 data is the same.Figure 11 shows the increasing along with speed, and the water yield of deviating from from paper web also increases.Figure 11 shows that also when nip pressure increased, if web speed is constant, the dehydrating amount in the paper web also increased, and therefore, when adopting two woollen blankets to squeeze the mold pressing paper web, must not carry out balance between dehydrating amount, web speed and nip pressure.Dehydrating amount has increased, and the rewetting of paper web alleviates, thereby has been maintained the associative key between fiber and the fiber, and the drying efficiency of paper machine has also improved, and improves web speed and can make paper web more economically.Increase the density that squeeze pressure can further improve the high density area 1083 shown in Fig. 4, thereby improve the TENSILE STRENGTH of mold pressing paper web.
Leaving theoretical question does not talk and can think: under high speed, the nip of single dehydration woollen blanket descends water separation capability, and this is that the rewetting situation of its exit paper web has increased the weight of in this nip because under high chart speed.As prior art discloses, exist a kind of vacuum in the exit of nip.Produce the reason of this vacuum, some reasons are the rapid separation at nip exit two roller surfaces at least.This vacuum that produces owing to the separation of roller surface will square increasing with the speed of roller surface, as following document discuss, these documents are used as reference at this: Drainage at a Table Roll, Taylor, Pulp and Paper Magazine of Canada, Convention Issue 1956, pp 267-176; And Drainage at a Table Roll and a Foil, Taylor.pulp and Paper Magazine of Canada, Convention Issue 1958, pp172-176.
With reference to Fig. 4, this vacuum phenomenon results between mold pressing paper web 120B and the pressure roller 322, and between mold pressing paper web 120B and the pressure roller 362.The vacuum that mold pressing paper web 120B and pressure roller are 322 also may be strengthened when dehydration woollen blanket 320 leaves nip in the expansion owing to this woollen blanket 320.If cancellation dehydration woollen blanket 360 is pressed into moisture the deflected channel portion 230 from woollen blanket,, might be pulled back in the surface 124 of embossed paper 120B owing to be positioned near the surface 122 of mold pressing paper web 120B vacuum action.The a part of reason that produces this vacuum is to remove from paper web in the exit of nip 300 and cause owing to pressure roller 322, and partly cause then is that the expansion of dehydration woollen blanket 320 in nip 300 exits causes.In contrast,, then can provide a kind of circulation path, in order to receive the moisture of from the deflected channel portion 230 of impression element 219, discharging than low capillary pipe size if comprise dehydration woollen blanket 360.Why current can enter dehydration woollen blanket 360 from deflected channel portion 230, and at least a portion reason is because in nip 300 exits, the vacuum that dehydration woollen blanket 360 is produced when impression element 219 is separated causes.Like this, when dehydration woollen blanket 360 exists, will there be very a spot of moisture to be present in the deflected channel portion 230 in the exit of nip.Equally, dehydration woollen blanket 360 is in the expansion in nip exit, increased near the total vacuum the surface 124 of mold pressing paper web 120B, like this, just helps the pressure of balance nip exit mold pressing paper web 120B two sides.
Except can preventing the rewetting of mold pressing paper web in nip 300, the applicant also finds, it helps to reduce to act on the shearing force on 300 paper webs of nip.By a suitable motor, drying drum 510 is rotated around its rotation with a predetermined speed, pass nip thereby drive paper web and impress element 219 with a predetermined speed.The shearing force that acts on the paper web may come from the speed difference that dewaters in the nip 300 between woollen blanket 320 and paper web and the impression element 219.This shearing force is very disadvantageous because they can influence between the fiber associative key and when squeezing formed mold pressing paper web structure.The shear action that paper web dewaters between the woollen blanket 320 relatively also may produce a vacuum between nip 300 dehydration woollen blankets 320 and paper web, cause that thus the water of discharging from deflected channel portion 230 is with paper web rewetting.
The applicant finds, pressure roller 322 and 362 is carried out single driving, so that make the roughly the same speed of dehydration woollen blanket 320,360, paper web and impression element 219 pass nip 300 along machine context, this just can at utmost reduce the shearing force of paper web.The single driving pressure roller just means that the torque of pressure roller 322 and 362 is provided by a driving mechanism respectively, rather than the frictional force that is produced in the pressured district 300.Like this, pressure roller 322 still is 362 not to be dummy roll.Pressure roller 322 and 362 can be driven by same motor, also can be driven by different motors.In a preferred embodiment, motor provides torque to make drying drum 510 rotations, and the speed when adjusting paper web and impression element 219 and passing nip 300.Two different motors, every links to each other with 362 with pressure roller 322 respectively, thereby makes the pressure roller rotation.Every motor all provides necessary torque so that relevant pressure roller overcomes friction load and the nip live load that acts on the pressure roller.The independent torque control of platen motor can be finished by the armature supply of controlling a d.c. motor, for example a kind of winding d.c. motor in parallel, and this motor can be from RelianceElectric Company ofCleveland, and Ohio buys.Or, also can come to transmit necessary torque by the torque output of controlling an AC speed regulating motor to pressure roller.The necessary torque that sends each pressure roller to will be depended on multiple factor, comprising but be not limited to: the type and the squeeze pressure that act on the friction load on the pressure roller.Can be by calculating the necessary torque of rough estimate.Also can determine the torque of pressure roller by experiment with the method for revising, promptly change the torque of pressure roller, the TENSILE STRENGTH of the measurement mode platen width of cloth is perhaps measured the water yield of discharging in the nip from paper web then.If ceteris paribus, when the shearing force of paper web hour, the TENSILE STRENGTH of mold pressing paper web is generally maximum.
The 6th step of the present invention can comprise the drying of giving to mold pressing paper web 120B, is for example undertaken by Tad machine shown in Figure 1 400.Can make a kind of dry air, for example hot-air passes mold pressing paper web 120B, thereby it is given drying.In one embodiment, hot-air at first passes mold pressing paper web 120B and arrives second paper 124 from first paper 122, and then passes the deflected channel portion 230 of the impression element 219 that is loaded with the mold pressing paper web.The air that passes mold pressing paper web 120B makes mold pressing paper web 120B part dry.In addition, leave theoretical question and do not talk, found to pass the air of the paper web part that links to each other with deflected channel portion 230, can make paper web further go in the deflected channel portion 230 partially, and reduce the density of low density area 1084, thereby improve bulkiness and the flexibility directly perceived of mold pressing paper web 120B.In one embodiment, mold pressing paper web 120B its concentration when entering Tad machine 400 is about 30～65%, and when leaving Tad machine 400, its concentration is about 40～80%.
With reference to accompanying drawing 1, Tad machine 400 can comprise a hollow going barrel 410.Mold pressing paper web 120B is loaded on the impression element 219 and rotates around hollow drum 410, and hot-air radially outwards flows from hollow drum 410, passes paper web 120B and impression element 219.Also can allow hot-air radially inwardly blow (not shown).Be fit to the Tad machine that the present invention uses and authorize the United States Patent (USP) 3,303,576 of Sisson in May 26 nineteen sixty-five, and authorized record to some extent in people's such as Ensign the United States Patent (USP) 5,274,930 on January 4th, 1994, these patents are used as reference at this.Also the drying equipment that one or more Tad machines 400 or other are fit to can be placed on the upstream end of nip 300, before paper web passes nip 300, it be carried out the part drying.
The 7th step of the present invention can comprise that the paper web impression face 222 that porous is impressed element 219 compresses into the mold pressing paper web, to form a kind of impression paper web 120C.Paper web stamping surface 222 is pressed into the density that can also further improve mold pressing paper web higher density district 1083 among the mold pressing paper web 120B, thereby the density contrast between the zone 1083 and 1084 is strengthened.With reference to Fig. 1, mold pressing paper web 120B is carried on the impression element 219, and is impressing between an element 219 and the press surface in nip 490.This press surface can comprise the surface 512 of heated drying drum 510, and nip 490 can form between pressure roller 209 and drying drum 510.Under the help of creping adhesives, the paper web 120C behind the impression is adhered on the surface 512 of drying drum 510, carries out last drying.When the impression paper web 120C of drying is removed following time from drying drum 510, it can be given contracts, and for example scrapes with a handle and cuts 524 and will impress paper web 120C wrinkling scraping from the drying drum.
It quantitatively is 10～65%m that method of the present invention is particularly suitable for being used for making 2About paper web.This paper web is suitable for being used for making individual layer and multi-ply tissue and tissue products.
That Figure 12 and 13A represent is the embodiment of another paper machine of the present invention, wherein removed Tad machine 400, in Figure 12, when mold pressing paper web 120B is carried on the impression element 219 when nip 300 leads to nip 490, second woollen blanket 360 is positioned near the second surface 240 of impression element 219.Nip 490 among Figure 12 is formed between pressure roller 299 and the Yang Keshi drying drum 510.Pressure roller 299 can be a vacuum pressure roller, and it is got rid of moisture from second woollen blanket 360 at nip 490.Pressure roller 299 also can be a solid roll, and by means of near second woollen blanket 360 the second surface 240 of impression element 219, mold pressing paper web 120B is carried on the impression element 219 and is sent to nip 490, so that mold pressing paper web 120B is sent to Yang Keshi drying drum 510.
What Figure 15 and 16 represented is the paper web that adopts paper machine embodiment shown in Figure 12 to make.Figure 15 is the plane of a paper surface 124, and this face is near that paper surface that impresses element 219 in nip 300.Paper web shown in Figure 15 is to adopt a kind of impression element 219 with deflected channel 230 of a continuous net-shaped paper web impression face 222 and a plurality of dispersions to make, paper web among Figure 15 has many low-density domes 1084, and they spread all within the whole highdensity continuous net-shaped district 1083.At least a portion dome 1084 among Figure 15 is by wrinkling process preshrunk.This can the wrinkle and the bending of some domes obtain proof from Figure 15.The contraction situation of dome 1084 can be seen more clearly in Figure 16, has wherein also demonstrated the contraction situation in continuous net-shaped district 1083.The section of Figure 16 is along being parallel to machine direction intercepting, and it has represented the contraction that causes owing to wrinkling.In Figure 16, the characteristics of the contraction of dome 1084 are the wrinkle 2084 that swept, and the characteristics of the contraction in continuous net-shaped district 1083 are the wrinkle 2083 that swept.Dome 1084 has certain wrinkling frequency (along 2084 numbers of the wrinkle on the machine direction unit length), and it is different from the wrinkling frequency (along 2083 numbers of the wrinkle on the machine direction unit length) in continuous net-shaped district 1083.
With reference to Figure 13 A and 13B, this paper machine has a kind of combined type impression element 219, and this element has the colored type photopolymerization layer 221 of paper web that a surface with dehydration woollen blanket 360 combines.Seeing on these layer 221 macroscopic views to be plane, is a continuous net-shaped paper web stamping surface 222 with certain colored type in fact.This combination impression element 219 can comprise a kind of lip-deep photopolymerization resin layer of dehydration woollen blanket that is moulded into.The U.S. Patent application No.08/268 that people such as Trokhan submitted on June 28th, 1994,154, its denomination of invention is for " the paper web flower type equipment that has a woollen blanket layer and a photosensitive resin layer " is used as reference at this, so that the structure of this combination impression element is described.The deflected channel 230 of photopolymerization layer 221 forms fluid communication with woollen blanket 360, shown in Figure 13 B.
In Figure 13 A, initial paper web 120 is transferred to the photopolymerization paper web stamping surface 222 of combination impression element 219.At nip 300, paper web is crushed between first woollen blanket 320 and the combination impression element 219, and the latter comprises the photopolymerization paper web stamping surface 222 and second woollen blanket 360.Subsequently, mold pressing paper web 120B is placed on the stamping surface 222 that makes up paper web impression element and delivers to nip 490.Nip 490 among Figure 13 A forms between pressure roller 299 and the Yang Keshi drying drum 510.Pressure roller 299 can be a kind of vacuum pressure roller, and at nip 490, it is extruded moisture from second woollen blanket 360.Though this pressure roller 299 also can be a solid roll.Combination impression element 219 is near the surface 124 of mold pressing paper web 120B, and paper web is placed on the combination impression element 219 and is sent to nip 490, so that mould district paper web 120B is sent to Yang Keshi drying drum 510.
Figure 17 and 18 has represented the paper web that adopts the paper machine shown in Figure 13 A to make.Figure 17 is the plan view of paper web face 124, and this surface is near that paper surface that impresses element 219 in nip 300.The paper web of Figure 17 is to make with a kind of impression element 219 with logical portion 230 of deflection of continuous net-shaped paper web stamping surface 222 and several dispersion.Paper web shown in Figure 17 has many low-density domes 1084, and they are scattered in the continuous net-shaped district 1083 of whole high density.In wrinkling process, at least a portion dome 1084 shown in Figure 17 has produced contraction, and this can obtain proof by the bending and the wrinkle of some domes from Figure 17.The contraction of dome 1084 is more clear in Figure 18, wherein also expressed the contraction in continuous net-shaped district 1083.The cross section of Figure 18 is to intercept along the direction that is parallel to machine, and it has expressed the contraction that forms owing to wrinkling.In Figure 18, the shrinkage characteristic of dome 1084 is wrinkle 2084, and the shrinkage characteristic in continuous net-shaped district 1083 is wrinkle 2083.The wrinkling frequency of dome 1084 (along 2084 numbers of the wrinkle on the machine direction unit length) is different with the wrinkling frequency (along wrinkle 2083 numbers of machine direction unit length) in continuous net-shaped district 1083.
The thickness of the various parts of fibrous structure sample and front view are by recording in the optical microphotograph picture of being cut into slices in the cross section of paper structure.A width of cloth optical microphotograph picture of in Figure 14, having represented the section of this cross section.This cross section section is to make from the pattern of a 2.54cm * 5.1cm (1 inch * 2 inches).This sample marks with some reference points, makes wherein so that determine section.With the centre of this sample nail at two cardboard sheet frames.This sheet frame downcuts from file Folding card material, and each cardboard frame all is about 2.54cm * 5.1cm.The about 0.25cm of the width of frame.The cardboard frame that will have sample is put into the silicon mould, and this mould has the pit of 2.54 * a 5.1 * 0.5cm.With a kind of resin, for example by Hercules, the Merigrph light polymers that Inc. makes injects the silicon mould that contains sample.Pattern is immersed in the resin fully, utilizes a kind of ultraviolet sample solidifies to become a kind of resin compound, the fortified resins that will contain sample take out, and framework is excised from resin mass, and sample is pruned so that can dissect with special blade.
Sample is placed on the Buffalo by American Optical Company of, cuts on the 860 type slicers that New York sells, the edge of sample is removed from sample, make it to become sheet, until presenting a smooth surface with slicer.
From sample, downcut the section of sufficient amount, so that can accurately rebuild various zone.For described embodiment, the thickness of these sections is about 100 microns/sheet, all is taken from smooth surface.Need produce several sections, so just can find out the thickness in variant zone.When measuring wrinkling back sample thickness, should intercept section along direction across machine.So just can avoid owing to interference that wrinkle causes (in order to express wrinkle, among Figure 16 and 18 cross-section) along the machine direction intercepting.
Utilize oil and cover plate that the sample section is placed on the microscope balladeur train.Balladeur train and sample all are placed on a kind of light and transmit on the microscope.For example by Nikon Instruments, the Nikon 63004 that Melville, NY provide #The type microscope disposes high-definition camera, with 10 times of object lens sample is observed.What the shooting microphoto that obtains from section adopted is that high-definition camera is (for example by Javlin Electronics, the Javelin JE 3662HR type that Los Angeles CA makes), the framework clamping plate can be used the Transition by Data, Marlboro, the Data Translations Frame Grabber Boad that MA makes, image software can be used NTIS, of Springfield, the NIH Image Version 1.41 that Virginia provides, data system can adopt Macintosh Quadra 840 AV.Obtain the shooting microphoto along section, then each shooting microphoto is arranged ordering.So that the shape of section is constructed again.The shooting microphoto is amplified to 6.75 inches * 9 inches, and hard copy is about 400 times.
Can be by a kind of suitable CAD (CAD) mapping software, for example the Power Draw edition 4 .0 that is provided by EngineeredSoftware of North Carolina sets up the thickness of area-of-interest.The shooting microphoto that obtains from image 1.4 is selected, duplicated, paste with Power Draw then, each light micrograph is arranged in order, so that rebuild the figure of section.Has a calibration yardstick by obtaining one, for example 1/100mm Objective Stage Micrometer N36121 (can be from EdmundScientific, Barrington, NJ obtains) the shooting microphoto, duplicate then and in CAD software, paste promptly and can carry out suitable calibration this system.
The thickness of any specified point of area-of-interest can pass through the circle of the maximum of being drawn to be determined, this circle can be placed on that specified point in this zone, and does not exceed the border of image, as shown in figure 14.At this this regional thickness of some place diameter that is exactly circle.In Figure 14, high density area 1083 comprises a continuous net-shaped district, and low density area 1084 then comprises low-density dome.
With reference to Figure 14, the thickness T of transition range 1073, the thickness K of high density area 1083, and the thickness P of low density area 1084 records according to following program.At first, be confined on the cross section, it has a high density area 1083, and this is distinguished at low density area 1084, and one is extended between near the transition range 1073 each end of high density area 1083.The transition range 1073 thickness minimums of each end of close high density area 1083, necking point is between high density area 1083 and low density area 1084.In Figure 14, made 1073A and 1073B by mark near the transition range of high density area 1083 each end.
Scan reaching 20 microsection sections, has high density area 1083 and near the section sections of the transition range 1073 of this each end of high density area, wherein so that fix five: near the 1) thickness in 1073 zones the thickness of the everywhere of regional 1083 parts all is greater than these 1083 each ends, zone; 2) thickness in the everywhere of regional 1083 parts all is less than the maximum ga(u)ge of low density area 1084, and extend between zone 1084 in zone 1083.If after 20 microsection plane of structures are described, 5 of this cross section less thaies that finds, this just illustrates that this sample does not contain transition range 1073.
The transition range 1073A of zone each end of 1083, maximum annulus 2011 of the tested work of the thickness of 1073B and 2012 diameter, this annulus is suitable for transition range 1073A and 1073B.Thickness T is the average of these two measured values.In Figure 14, annulus 2011 and 2012 diameter are respectively 0.043mm and 0.030mm, and like this, the T value in cross section is 0.036mm among Figure 14.The thickness K of the high density area 1083 that extends between regional 1073A and 1073B determines at next step.Distance L between two annulus 2011 and 2012 is measured (being about 0.336mm among Figure 14).Be positioned at half place of annulus 2011 and 2012 centre-to-centre spacing in the annulus 2017.Annulus 2018 and 2019 the right side that is centered close to annulus 2017 centers and the L/8 place in left side, the thickness K in zone 1083 is the average diameter of three annulus 2017～2019.In Figure 14, the diameter of these annulus is respectively 0.050mm, 0.050mm and 0.048mm, and like this, thickness K just is about 0.049mm.Thickness P is regarded as in the low density area 1084 the local maximum ga(u)ge till the left side of regional 1073A, and the local maximum ga(u)ge till the right side of regional 1073B.For cross section shown in Figure 14, thickness P equals the diameter of annulus 2020, is about 0.091mm.For section shown in Figure 14, this value T/K is 0.036/0.049=0.74.For section shown in Figure 14.This value P/K is 0.091/0.049=1.8, and this value of above-mentioned thickness T/K is the mean value of the T/K ratio of 5 sections.Thickness ratio P/K then is the mean value of the P/K of same 5 sections.
At this, total TENSILE STRENGTH (TT) is meant along machine direction with across the quantitative (g/m of machine direction maximum intensity sum (g/m) divided by sample 2) value of gained.The numerical value of TT is represented with rice.Adopt a kind of tension test machine, for example by Thwing-Albert, the Intelect II STD that Philadelphia, Pa provide can measure its maximum intensity.For the sample of wrinkling mistake, when measuring maximum intensity, its crosshead speed (cross head speed) is 1 inch per minute, then is 0.1 inch per minute to not wrinkling handmade paper sample.For handmade paper, only survey the maximum intensity of its machine direction, it is quantitative divided by it that the value of TT equals two times of maximum intensity of its machine direction.The numerical value TT that is quoted is the mean value of at least 5 measurement data.
Paper web stiffness described herein is meant the tangent slope of curve of power (with g/cm sample width means) and the ratio of its strain (every centimetre of elongation cms of measuring length).Along with reducing of slope, the flexibility of paper web improves and stiffness decline.For the sample of wrinkling mistake, its slope is for obtaining when the power of 15g/cm, and to without wrinkling sample, its slope then obtains under the condition of 40g/cm power.These data can be utilized Thwing-Albert, Philadelphia, the Intelect II STD strength test machine that Pa provides records, sample for wrinkling mistake, its crosshead speed is 1 inch per minute, and the sample width is about 4 inches, and for without wrinkling handmade paper, the sample that then is respectively 0.1 inch per minute and 1 inch is wide, and total stiffness index described herein (TS) is meant the geometric mean of the tangent slope of the tangent slope of its machine direction and cross-machine direction.On mathematical definition, it is the square root of the tangent slope product of the tangent slope of machine direction and cross-machine direction, represents with g/cm.For handmade paper, only measure its slope along machine direction, the value of TS is taken as the slope of its machine direction, and the TS value of being quoted is the mean value of at least 5 measured values.In table 1 and 2, TS is by total tension force (Total Tensile) standardization, so that a kind of deflection index TS/TT of standard is provided.
Macroscopic thickness described herein is meant the macroscopic view observation thickness of sample.Sample is placed on the plane of a level, and is placed between this flat surfaces and the load presser feet, presser feet has the load surface of a level, and the load meter mask of this load presser feet has an area to be about 3.14 inches 2The circular surface district, and sample applied an about 15g/cm 2Restriction pressure (0.21psi).This macroscopic thickness results from the gap between described flat surfaces and the load presser feet load surface.These data can adopt by Thwing-Albert, and the VIR Electronie Thikness Tester Model II that Philadelphia, Pa provide obtains, and this macroscopic thickness is the mean value of at least 5 numerical value.
The weight that quantitatively is meant a thin paper sample unit are described herein, its unit is g/m 2
Apparent density described herein is meant the quantitative value divided by the macroscopic thickness gained with sample.
Embodiment 1:
The purpose of present embodiment is to adopt the Tad method to produce method soft, bibulous paper handkerchief to describe to a kind of, the chemical flexibilizing agent that this paper web adopts a kind of Di of containing (hydrogenation) Tallow Dimethyl AmmoniumChloride (DTDMAC), Polyethylene glycol 400 (PEG-400) and a kind of long-acting hygrometric state to strengthen the mixture of resin is handled, and adopts method of the present invention to squeeze then.
The present invention adopts a bench teat to test the fourdrinier machine of scale, as shown in Figure 1.At first, the method for authorizing example 3 in people's such as Phan the United States Patent (USP) 5,279,767 according on January 18th, 1994 is prepared a kind of chemical flexibilizing agent of 1% concentration.In second step, utilizing traditional pulper to produce weight concentration is 3% NSK water slurry.NSK slurry is made with extra care, and be that 2% long-acting hygrometric state strengthens resin (promptly by Hercules in corporatedofWilmington, the Kymene 557H that DE sells) and joins in the NSK slurry pipe in the ratio of fiber dry weight 1% a kind of concentration.Kymene 557H is strengthened by a kind of on-line mixing device the surperficial absorption of NSK.After carrying out on-line mixing, add concentration again and be 1% Carboxy MethylCellulose (CMC), so that improve the dry strength of fibre substrate with the ratio of dry fiber weight 0.2%.CMC also can be strengthened by a kind of on-line mixing device to the surperficial absorption of NSK.Then, be that 1% chemical softening mixture (DTDMAC/PEG) adds in the NSK slurries with the ratio of dry fiber weight 0.1% with a kind of concentration.The soft gentle mixture of this chemistry can be strengthened by an on-line mixing device to the surperficial suction-operated of NSK.By means of a desk fan page or leaf pump NSK will be diluted to 0.2%.In the 3rd step, in traditional pulper, produce weight concentration and be 3% CTMP water slurry.Ratio according to dry fiber weight 0.2% adds a kind of nonionic surface active agent (Pegosperse) in the pulper.Adding concentration in the ratio of fiber dry weight 0.1% in the CTMP slurries pipeline before pulp pump again is 1% chemical softening mixture.The chemical softening mixture can be strengthened by the on-line mixing device to the surperficial suction-operated of CTMP.By fan page or leaf pump the CTMP slurry is diluted to 0.2%.The ingredients mixture of handling (NSK/CTMP) is sneaked into head box, and make it to be distributed on the fourdrinier wire 11, thereby form initial paper web 120.Under the cooperation of water fender and vacuum tank, dewater by fourdrinier wire.This fourdrinier wire is the fabric of the satin face configuration of 5 shed opens (shed), and along on machine direction and the cross-machine direction, its single thread density is respectively 84 pieces/inch and 76 pieces/inch.Initial paper web is gone to impression element 219 by fourdrinier wire, be about 22%, on the paper web contact-making surface 220 of impression element 219, have about 240 interlaced oval-shaped deflected channel 230 per square inch in the concentration of branchpoint place fiber.The major axis of oblong deflected channel is roughly parallel to machine direction.The degree of depth of deflected channel 230 is approximately 14 mils.Impression element 219 has a continuous net-shaped photopolymer paper web stamping surface 222.The surface area of continuous net-shaped paper web stamping surface 222 is about about 34% (i.e. 34% joint area) of paper web contact-making surface 220 surface areas.
By means of a vacuum aided dewater unit paper web is further dewatered, reach about 28% until its fibre concentration, at nip 300, the paper web 120A that has certain colored type of non-monoplane shape is pressed between two woollen blankets by the pressure with about 250 PSI.The fibre concentration of the mold pressing paper web 120B that generates is about 34%.By means of Tad device 400 with the predrying weight concentration to about 65% of paper web.By a kind of sprinkling creping adhesives that contains 0.25% polyvinyl alcohol (PVA) aqueous solution paper web is adhered on the surface of Yang Keshi drying drum 510 then.With wing paper web is carried out dry state wrinkling before, the concentration of fiber is increased to about 96%.The oblique angle of scraper is about 25 degree, with respect to Yang Keshi drier location, thereby constitutes one 81 angle of attack about degree.The rotating speed of Yang Keshi drier is about 800fpm (feet per minute) (being roughly equal to 244 meters/minute).The speed of the 700fpm (214 meters/minute) of dried paper web is rolled into a paper bowl.
The character of the squeezing paper web that makes according to embodiment 1 (pressure is 250psi) is listed in the table 1.Adopt identical batching, identical paper web conveyer and paper web impression element 219, but also in table 1, list without the corresponding character of the base web of squeezing, so that compare.Specifically, the standard stiffness index of paper web after squeezing is less than the paper web without squeezing, and its total TENSILE STRENGTH the former to be higher than the latter.
Two layers or more multi-layered squeezing paper web combined to form a kind of multi-layered product.For example, can carry out embossing and lamination to paper web, be combined into a kind of double-deck paper handkerchief thereby make embodiment 1 prepared two laminations press paper web by the PVA adhesive.In the paper handkerchief that makes, contain the chemical softening mixture of about 0.2% weight and the long-acting hygrometric state of 1.0% weight and strengthen resin.This paper handkerchief softness, its absorbability are as by two layers of double-deck paper handkerchief of making of base web without squeezing, and its intensity will be higher than it.
Embodiment 2:
The purpose of this embodiment is to describe a kind of technology that adopts the papermaking of Tad method, produce soft, that absorbent properties are good, can be for the method for the paper web of making the paper handkerchief use.With the chemical softening composition that a kind of Di of including (hydrogenation) Tallow Dimethyl Ammonium Chloride (DTDMAC), a kind of Polyethylene glycol 400 (PEG-400), a kind of long-acting hygrometric state strengthen resin compound paper web is handled, squeeze with the high squeeze force greater than embodiment 1 then, air penetration formula paper machine as shown in Figure 1.
Except nip pressure was 300PSI, the forming process of paper web was identical with embodiment 1.The character of the squeezing paper web that makes according to embodiment 2 is listed in the table 1.Utilize the PVA adhesive can be, thereby make two layers or more multi-layered squeezing paper web be combined into a kind of multi-layered product paper web embossing and laminated together.The double-deck paper web that two layers of squeezing paper web that is made by embodiment 2 is combined and make is very soft, the double-deck paper handkerchief that its absorbability combines and makes as the squeezing paper web that two layers are made by the method for embodiment 1, and its intensity will be higher than it.
The character of the wrinkling paper handkerchief width of cloth of table 1
The base web squeezing paper web pressed paper width of cloth that character is not squeezed
250PSI (example 1) 300PSI (example 2)
TT(m) 1532 2165 2200
TS/TT 6.41 4.81 5.07
Quantitative g/m 222.0 21.8 21.9
Apparent density kg/m 351.0 49.3 50.2
Transition range thickness (mm) 0.061 0.037 0.032
Joint thickness (mm) 0.067 0.056 0.052
Plate thickness (mm) 0.131 0.117 0.143
T/K 0.91 0.67 0.63
P/K 1.91 2.26 2.78
Macroscopic thickness (mm) 0.43 0.44 0.44
Embodiment 3:
In the described thin paper production process of present embodiment, do not use air penetration formula drying machine.The present invention has adopted a kind of fourdrinier machine of experimental size, and this paper machine as shown in figure 12.Simply say, a kind of first fiber pulp consists predominantly of papermaking short fiber, it with consist predominantly of long stapled second fiber pulp of papermaking and mix mutually, utilize pump that they are sent in the head box chamber, make it then to be distributed on the fourdrinier wire, form a kind of initial paper web, the fibre concentration of first fiber pulp is about 0.11%, and its fibre composition is the eucalyptus BHKP.The fibre concentration of second fiber pulp is about 0.11%, and its fibre composition is the northern softwood kraft pulp.The ratio of eucalyptus and northern softwood is approximately 60/40.Dewater and help with fourdrinier wire with water fender and vacuum tank.This fourdrinier wire is the satin face configuration fabric of 5 shed opens, is divided into 87 pieces/inch and 76 pieces/inch along the radical of machine direction and cross-machine direction per inch single thread.
Initial wet web is gone to paper web impression element 219 from fourdrinier wire, and the fibre concentration at the branchpoint place is about 22%.Impression element 219 has about 240 crisscross oval deflected channel 230 per square inch on its paper web contact-making surface 220, the major axis of oval deflected channel is roughly parallel to machine direction, and the degree of depth 232 of deflected channel 230 is about 14 mils.This impression element 219 has the paper web impression face 222 of a continuous net-shaped photopolymer.The surface area of this continuous net-shaped paper web impression face 222 is about 34% (34% hinge area) of paper web contact surface 220 surface areas.
With vacuum dewatering plant paper web is done further dehydration, make it fibre concentration and reach about 28%.The paper web 120A that has colored type that this is non-planar is clipped between first and second dehydration woollen blanket 320 and 360, and it is applied about 250 PSI pressure.The fibre concentration of the mold pressing paper web 120B that generates is about 34%.By means of second woollen blanket 360 near the second surface 240 that impresses element 219, mold pressing paper web 120B is being carried by impression element 219 and is entering nip 490, so that it is sent to Yang Keshi drying drum 510.
By what spray, the creping adhesives that wherein contains 0.25% polyvinyl alcohol (PVA) aqueous solution is bonded at paper web on the surface of Yang Keshi drier.With scraper paper web is carried out dry state wrinkling before, about its fibre concentration height to 96%, the inclination angle of wing is about 25 degree, the Yang Keshi drier is placed relatively, so that angle of attack is reached about 81 degree.The speed of Yang Keshi drier is 800fpm (feet per minute) (being about 244 meters/minute).Speed with 700fpm (214 meters/minute) is rolled into roller with dried paper web.
It quantitatively is 16g/m through squeezing wrinkling tissue paper product 2, its TENSILE STRENGTH is greater than with identical batching and impression element 219 and produces, and the low-density dome district of formed wrinkling paper web 1084 is by preshrunk, and its wrinkling frequency is different with continuous net-shaped high density area 1083.Its final structure is shown in the plan view photo of Figure 15, and the light micrograph in the cross section of this structure as shown in figure 16.
Embodiment 4:
What this embodiment described is not use the Tad machine to produce the process of double-deck tissue paper product.What adopt when enforcement is of the present invention is a kind of fourdrinier machine of experimental size.Paper machine shown in Figure 13 A has a stacked head box, and it has a upper chamber and a lower chambers.Put it briefly, a kind of first fiber slurry based on papermaking short fiber was pumped dirty slurry chamber, simultaneously, a kind of is that second fiber slurry of main component was pumped upper reaches slurry chamber with the papermaking long fiber, they are sent on the fourdrinier wire with stacked form, thereby form a kind of initial paper web of bilayer.The fibre concentration of first slurries is about 0.11%, and its fibre composition is the eucalyptus BHKP.The fibre concentration of second slurries is about 0.15%, and its fibre composition is the northern softwood kraft pulp.One dewatering plate and vacuum tank play booster action to the dehydration of passing fourdrinier wire and carrying out.This fourdrinier wire is the satin face configuration fabric of 5 shed opens, and the number of threads of per inch is respectively 87 and 76 on machine direction and cross-machine direction.
The initial wet paper web is sent to a compound impression element 219 from fourdrinier wire, at branchpoint place fibre concentration is about 10%, the impression element has a photopolymer layer that links to each other with the surface of dehydration woollen blanket 360, this light polymers layer has one and is macroscopical plane, the continuous net-shaped paper web stamping surface 222 of wounded in the battle type.Paper web turns to the process of compound impression element 219 to be cooperated by a vacuum paper injection chopping board (pick up shoe) 126 from fourdrinier wire.The continuous net-shaped paper web stamping surface 222 of photopolymer layer has several dispersion, isolated discrete deflected channel.The colored type of this deflected channel is identical with embodiment's 1, and the thickness of photopolymer layer is counted from the surface of woollen blanket 360 and is about 14 mils.
The paper web that is transmitted by vacuum is non-planar, and it has a kind of and paper web stamping surface 222 corresponding colored types.The fibre concentration of this paper web is 24%.The paper web that has colored type that this is non-planar brings to nip 300 by compound paper web impression element 219, is crushed between first woollen blanket 320 and the compound impression element 219, and this impression element also comprises second woollen blanket 360.The pressure of paper web during by nip is approximately 250 PSI.
The fibre concentration of the mold pressing paper web 120B that is generated is about 34%.Stick on the surface of a Yang Keshi drier by means of the creping adhesives of the aqueous solution that contains 0.25% polyvinyl alcohol (PVA) that is sprayed.With a wing paper web is carried out dry state wrinkling before, the concentration of fiber increases to about 96%.The inclination angle of wing is about 25 degree, and the Yang Keshi drier is placed relatively, to form an angle of shock that is about 81 degree.The speed of Yang Keshi drier is about 800fpm (inch per minute) (being about 244 meters/minute).Dried paper web becomes roller with the speed of 700fpm (214 meters/minute).
This wrinkling tissue paper product through squeezing quantitatively be about 16g/m 2, its TENSILE STRENGTH is greater than with same ingredients and impression element and makes, but the basic thin paper that but between two woollen blankets, did not carry out squeezing.The low-density dome 1084 of the wrinkling paper web that is generated is by preshrunk, its wrinkling frequency be the different of continuous net-shaped high density area 1083.One plane picture of the structure that shown in Figure 17 is is generated.Figure 18 then is a width of cloth optical microphotograph cross section picture of this structure.
Embodiment 5:
What this embodiment described is the production process of not using the not wrinkling paper product of Tad machine manufacturing.30 gram northern softwood are dissociated in 2000ml water.Paper pulp after will dissociating then dilutes in the dispenser of 000ml 1, and the weight that makes its dried fiber is 0.1%.The thin pulp that volume is about 2543ml adds in the deckle case that contains 20 premium on currency.The bottom of this deckle case has one 13.0 inches * 13.0 inches monofilament polyester plasticity fourdrinier wire, and this material is provided by Appleton Wire Co.Appleton Wisconsin.This net is the fabric of 5 shed open satin face configurations, is respectively 84 and 76 along the single thread number of per inch on machine direction and the cross-machine direction.The metal deckle box column plug of one porous from shifting to the bottom of paper pulp near the top of paper pulp, and is finished three circulations up and down back and forth, fiber pulp is distributed equably.Be approximately for 2 seconds the above-mentioned circulation timei that moves up and down.Then plunger is slowly extracted out, paper pulp just filters by net.After paper pulp is anhydrated by net, the deckle case is opened and net and fiber mat are taken out.The net that comprises wet web was dragged the vacuum notch to remove moisture.The peak value of vacuum is about 4 mercury column.The initial wet paper web is transferred on the impression element from network, and the fibre concentration at the branchpoint place is about 15%, and the length of impression element and the length and width of wide and silk screen are about equally.
The impression element has one and is continuous net-shaped photopolymer paper web stamping surface 222.On the paper web contact-making surface 220 of this impression element, nearly per square inch 300 crisscross lazy circular deflected channel 230.The major axis of this ellipse deflected channel is roughly parallel to machine direction.The degree of depth of deflected channel 230 is approximately 14 mils.The surface area of continuous net-shaped paper web stamping surface 222 is about 34% (34% hinge area) of the surface area of paper web contact-making surface 220.
When shifting, impression element, paper web and fourdrinier wire form the structure of a kind of " sandwich " formula, and this " sandwich " hauled passes a vacuum notch, thus the transfer process of finishing.The peak value of vacuum is about 10 mercury height.Fourdrinier wire is taken off from " sandwich ", the non-planar paper web that has colored type is bearing on the impression element, the fibre concentration of paper web is about 20%.Then paper web and impression element are clipped between two woollen blankets, with the pressure of 250 PSI to pressurization.The fibre concentration of the mold pressing paper web that generates is about 40%.By making the squeezing paper web be able to drying with contacting of steam drying drum.
The quantitative of the dried paper web that generates is 26.4g/m 2The TENSILE STRENGTH of the scraps of paper through squeezing is greater than and adopts identical batching, silk screen, impression element and jump condition, but the TENSILE STRENGTH of the basic scraps of paper that between two woollen blankets, the basic scraps of paper do not squeezed.The comparing data of this embodiment is listed in the table 2.
The character of the write by hand paper web that table 2 is not wrinkling
Character base paper 250 PSI squeeze (embodiment 5)
TT(m) 2414 3774
TS/TT 50 33
Quantitative (g/m 2) 26.8 26.8
Apparent density kg/m 3165 133
Transition range thickness (mm) does not observe 0.033
Hinge area thickness (mm) 0.069 0.056
Plate thickness (mm) 0.108 0.097
T/K na 0.59
P/K 1.56 1.73
Macroscopic thickness (mm) 0.16 0.20
Now instantiations more of the present invention are explained and are illustrated, still, for the person of ordinary skill of the art, under the prerequisite that does not break away from concept of the present invention, to can make all changes and distortion, this point is clearly.

Claims (20)

1, a kind of paper web, it comprises:
First a higher density district with first thickness K;
One have the second thickness P second than low density area; And
The 3rd district of extending in first and second district, the 3rd district comprises a transition range near first district, this transition range has the 3rd thickness T;
It is characterized in that its thickness than P/K greater than 1.0, and thickness than T/K less than 0.90.
2, paper web as claimed in claim 1, it is characterized in that its thickness than T/K less than 0.80.
3, paper web as claimed in claim 2, it is characterized in that its thickness than T/K less than 0.70, preferably less than 0.65.
4, as claim 1,2 or 3 described paper webs, its special sheet is that its thickness is at least 1.5 than P/K.
5, paper web as claimed in claim 4 is characterized in that the ratio P/K of its thickness is at least 1.7, preferably is at least 2.0.
6, as claim 1,2,3,4 or 5 described paper webs, it is characterized in that this paper web quantitatively be 10～65 grams/square metre between, its macroscopic thickness is at least 0.10mm, it is better to be at least 0.20mm, it is best to be at least 0.30mm.
7,, it is characterized in that having at least in first and second zone one by preshrunk as claim 1,2,3,4,5 or 6 described paper webs.
8, paper web as claimed in claim 7 is characterized in that second district is by preshrunk.
9,, it is characterized in that its first higher density district comprises a continuous net-shaped district as claim 1,2,3,4,5,6,7 or 8 described paper webs; And its second than low density area comprise some dispersions than the low-density dome, they are dispersed in the continuous net-shaped district, are separated from each other by continuous net-shaped district.
10, paper web as claimed in claim 9 is characterized in that than the low-density dome by preshrunk.
11, a kind of method that forms paper web, it comprises the steps:
A kind of aqueous dispersions of paper fibre is provided;
A kind of porous formed element is provided;
A kind of first dehydration woollen blanket is provided;
A kind of second dehydration woollen blanket is provided;
A nip is provided, and it is between first and second opposed press surface;
A kind of porous impression element is provided, and it has the paper web contact-making surface that comprises a paper web stamping surface, also has a deflected channel portion;
Make paper fibre at the initial paper web of porous formed online formation, this initial paper web tool has first and second surface;
Initial paper web is transferred on the porous impression element from porous formed element, made the paper web contact surface of the second surface of initial paper web near porous impression element;
A part of paper fibre of initial paper web is gone in the deflected channel partially, and from initial paper web, remove moisture, with paper web in the middle of the non-planar paper fibre that forms not squeezing by deflected channel;
Paper web is clipped between first and second woollen blanket sends into nip, it is characterized in that the first surface of first woollen blanket near middle paper web, the paper web stamping surface is near the second surface of middle paper web, deflected channel and the communication of the second woollen blanket layer fluid; And
Paper web in the middle of the squeezing is further gone in the deflected channel paper fibre partially in nip, makes paper web enrichment in the middle of the part, and from first and second surface dewatering of middle paper web, forms the mold pressing paper web.
12, method as claimed in claim 11 is characterized in that further comprising the steps of:
, by after the nip first surface of the first dehydration woollen blanket from the mold pressing paper web separated at the mold pressing paper web;
, by after the nip mold pressing paper web is supported on the paper web stamping surface at the mold pressing paper web;
One press surface is provided;
The mold pressing paper web is clipped in the middle of a paper web stamping surface and the press surface, thereby the paper web stamping surface is pressed in the mold pressing paper web, to form a kind of impression paper web; And
To impress the paper web drying.
13, method as claimed in claim 12 when it is characterized in that the paper web stamping surface is pressed into the mold pressing paper web, should make the paper web stamping surface between the mold pressing paper web and second woollen blanket.
14, as claim 11,12 or 13 described methods, it is characterized in that impressing element and comprise compound impression element, it has the paper web stamping surface that combines with the second woollen blanket layer.
15, as claim 11,12,13 or 14 described methods, it is characterized in that the nip pressure to middle paper web is at least 100psi in nip, better between 200～1000psi.
16,, it is characterized in that also being included under the situation of concentration 10～20% initial paper web is transferred to porous impression element as claim 11,12,13,14 or 15 described methods.
17, as claim 11,12,13,14,15 or 16 described methods, when it is characterized in that squeezing the centre paper web, at the population place of nip, its concentration is between 14～80%, and 15～35% is better.
18, as claim 11,12,13,14,15,16 or 17 described methods, it is characterized in that impressing element and have a paper web contact-making surface, it comprises that a macroscopic view is the continuous net-shaped paper web impression face of plane wounded in the battle type, paper web impression face limits some dispersions in porous impression element, isolate mutually, disconnected deflected channel, this method is further comprising the steps of: in nip middle paper web is squeezed, to form a mold pressing paper web, it has the continuous net-shaped paper web embossed region that a macroscopic view is plane wounded in the battle type, this district's density is higher, the dome that also has some dispersions, its density is lower, and dome is distributed in the webbed region of whole continuous higher density, is kept apart by the higher density webbed region each other.
19, as claim 11,12,13,14,15,16,17,18 or 19 described methods, it is characterized in that also comprising the step of paper web being carried out preshrunk.
20, method as claimed in claim 18 is characterized in that also comprising the step that continuous net-shaped district and some dispersion domes that is distributed in the continuous net-shaped district are carried out preshrunk.
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CN103410045B (en) * 2013-08-15 2016-04-20 金红叶纸业集团有限公司 Paper and preparation method thereof
CN106968121A (en) * 2015-10-05 2017-07-21 安德里特斯公开股份有限公司 Method for manufacturing fiber material web
CN106968121B (en) * 2015-10-05 2019-10-25 安德里特斯公开股份有限公司 Method for manufacturing fiber material web
CN113329868A (en) * 2019-01-22 2021-08-31 卓德嘉表层保护有限责任公司 Film for use as an interlayer between substrates
CN113329868B (en) * 2019-01-22 2024-01-09 卓德嘉表层保护有限责任公司 Film as an inter-substrate layer

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CZ183596A3 (en) 1996-11-13
NO308804B1 (en) 2000-10-30
US5637194A (en) 1997-06-10
CN1070964C (en) 2001-09-12
BR9408381A (en) 1997-08-26
DE69417068T2 (en) 1999-08-05
AU710051B2 (en) 1999-09-09
NO962572D0 (en) 1996-06-18
DK0741820T3 (en) 1999-09-27
KR100339664B1 (en) 2002-11-27
ES2128705T3 (en) 1999-05-16
WO1995017548A1 (en) 1995-06-29
CA2178586C (en) 2000-07-04
CA2178586A1 (en) 1995-06-29
US5580423A (en) 1996-12-03
JP3217372B2 (en) 2001-10-09
EP0741820A1 (en) 1996-11-13
AU701610B2 (en) 1999-02-04
US5846379A (en) 1998-12-08
AU1374595A (en) 1995-07-10
NO962572L (en) 1996-08-19
AU1005099A (en) 1999-02-25
KR960706586A (en) 1996-12-09
FI962597A (en) 1996-07-26
GR3029721T3 (en) 1999-06-30
EP0741820B1 (en) 1999-03-10
ATE177490T1 (en) 1999-03-15
JPH09506937A (en) 1997-07-08
FI962597A0 (en) 1996-06-20

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